Materials which can provide patchouli-like, amber and woody fragrance notes are known in the art of perfumery. Many of the natural materials which provide such fragrance and contribute desired nuances to perfumery compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
There is accordingly a continuing effort to find synthetic materials which will replace the essential fragrance notes provided by natural essential oils or compositions thereof. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the compositions. The search for materials which can provide a more refined patchouli-like fragrance has been difficult and relatively costly in the areas of both natural products and synthetic products.
Buchi et al., 83 J. Am. Chem. Soc. 927 (1961), shows the production of a material called "patchoulione" which is stated to be octahydro-1,4,9,9-tetramethyl-3a,7-methanoazulen-5(4H)-one having the structure: ##STR2##
U.S. Pat. No. 3,748,284 issued on July 24, 1973 discloses perhydro derivatives of methanoazulene as having camphoraceous woody fragrances and having the ability to impart this fragrance to perfumed compositions and perfumed articles. The compounds disclosed are:
a. Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-3(2H)-one having the structure: ##STR3## b. Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-2(3H)-one having the structure: ##STR4## c. Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-8(7H)-one having the structure: ##STR5## PA1 2. German Offenlegungschrift 2,242,913 published Mar. 8, 1973 PA1 3. Dutch published Application 72/11760 published Mar. 5, 1973 PA1 A. the compound having the structure: ##STR16## This compound has a warm patchouli-like fragrance aroma. B. ##STR17## This compound has a warm patchouli fragrance. PA1 3-Methylpent-4-yn-1-o1 PA1 3-Methylpent-4-yn-1-chloride PA1 3-Methylpent-4-yn-1-bromide PA1 Pent-4-yn-1-o1 PA1 Pent-4-yn-1-chloride PA1 Pent-4-yn-1-bromide PA1 2,6,6-Trimethylcyclohexadien-1-one PA1 2,3,4,5,6,6-Hexamethylcyclohexadien-1-one PA1 2,3,4,6,6-Pentamethylcyclohexadien-1-one PA1 6,6-Dimethylcyclohexadien-1-one PA1 4,5,6,6-Tetramethylcyclohexadien-1-one PA1 2,4,5,6,6-Pentamethylcyclohexadien-1-one
Umarani et al., Sept./Oct. 1969, P. & E. O. R., 307 discloses two compounds relevant to the instant case: "isopatchoulinol" having the structure: ##STR6## and "patchouli alcohol" having the structure: ##STR7##
Mirrigton and Schmalzl 37 J. Org. Chem. No. 18, 1972, pages 2871-2877 discloses the isolation of (-) patchouli alcohol having the structure: ##STR8## An article by Corey and Wipke entitled "Computer-Assisted Design of Complex Organic Syntheses" appearing in 166 Science 178 (1969) sets forth, interalia, the sequence of reactions leading to compounds having the structures: ##STR9## One of these reaction sequences involves performing the reactions: ##STR10## However, syntheses of methyl homologues and double compound isomers and an analogues patchouli alcohol and dihydropatchouli alcohol have not yet been disclosed in the prior art. Indeed, economic syntheses of patchouli alcohol itself do not appear to be given in the literature.
Danishevsky and Dumas 1968 Chemical Communication, Pages 1287-1288 discloses the synthesis of racemic patchouli alcohol and epi patchouli alcohol having the structure: ##STR11## by means of cyclization of a compound having the structure; ##STR12##
The use in perfumery of the compound having the structure: ##STR13## ("dehydro-norpatchoulinol") is disclosed in the following patents: 1. Belgium 788,301 issued Mar. 1, 1973
A product of the reduction of this compound is also disclosed ("norpatchoulinol"). This product has the structure: ##STR14## The compounds of our invention have properties considered to be unobvious, unexpected and advantageous with respect to the properties of the above-mentioned prior art compounds.